Geminal dinitro diaza dinitriles



GEMINAL DINITRO DIAZA DINITRILES Clinton R. Vanneman, Claremont, andKarl Klager, Monrovia, Califl, assignors to Aerojet-General Corporation,Azusa, Calif., a corporation of Ohio No Drawing. Application September6, 1955 Serial No. 532,729

13 Claims. (Cl. 260-4655) This invention relates to new compositions ofmatter and a method for their preparation. In particular, it relates togeminal dinitro-diaza-dinitriles having the general formula:

for the preparation of their corresponding diisocyanates.

The nitriles of this invention react with nitric acid to formnitraza-dinitriles, as disclosed in our copending application No.532,730, filed concurrently with the present application. Thenitrazadinitriles can be hydrolyzed in acid media to produce theircorresponding.

nitraza acids, as disclosed in our copending application No. 532,731,filed concurrently with the present application. The diacids thusobtained can be converted to their corresponding diisocyanatederivatives by conversion to the diazide followed by pyrolysis accordingto the method disclosed in our copending application Serial No. 451,707,filed August 23, 1954, now abandoned.

The diisocyanates thus obtained react with polyalcohols such as ethyleneglycol and 3,3-dinitro-l,S-pentanediol, in the presence of a catalystsuch as boron trifluoride, to yield high molecular weight polyurethanecompositions useful as solid propellants, according to the methoddisclosed in assignees copending application Serial No. 422,649, filedApril 12, 1954, now abandoned. The polyurethanes can be cast or pressedinto a suitable shape, usually a cylinder, and placed in a conventionalrocket chamber. To produce thrust for propulsion, the propellant issimply ignited whereby large quantities of gases are produced whichimpart forward thrust to the rocket upon exhaustion. The propellant canbe ignited by any conventional igniter, as for example the igniterdisclosed in assignees copending application Serial No. 306,030, filedAugust 23, 1952.

The compounds of this invention are prepared by condensing acrylonitrilewith a gerninal dinitro amine, in

accordance with the general reaction scheme set forth below:

wherein A and A are lower alkylene radicals.

The diamines used as starting materials for this invention are preparedby reacting a strong mineral acid with ageminal-dinitro-alkane-dicarbamate, as disclosed in as- Paten signeescopending application No. 428,790, filed May 10, 1954, now abandoned.

To more clearly illustrate this invention, the following examples arepresented. It is to be understood, however, that these examples arepresented merely as a means of illustration, and are not intended tolimit the scope of the invention in any way.

EXAMPLE I Preparation of 7,7-dinitro-4,10-diaza-1,13-tridecane dinitrileTo a solution of 82 gm. (0.5 mole) 3,3-dinitro-L5- pentane diamine in 45ml. methanol, 53 gm. (1 mole) acrylonitrile was added with stirringduring a 10 minute period. The temperature rose from 27 to 40 C. duringthis addition and continued to rise to a maximum of 58 C. within 20minutes. The solution was warmed briefly at gentle reflux temperaturebefore the solvent was distilled under reduced pressure. The crude7,7-dinitro- 4,10-diaza-1,13-tridecane dinitrile was an oil and weighed120 gm., corresponding to an 80.5% yield.

The particular temperatures and proportions employed in the aboveexample are not critical in the practice of this invention. Otherproportions as well as other temperatures can be used, however, lowertemperatures re- I quire longer reaction times; higher temperaturespermit shorter reaction times but tend to make the reaction morediflicult to control. 7

The preparation of the new compositions of this n vention may beconducted in the presence of an inert organic solvent. i

A wide variety of dinitriles can be prepared by following the procedureset forth in Example I. For example,8,8-dinitro-4,12-diaza-1,15-pentadecane dinitrile is prepared bycondensing 4,4-dinitro-1,7-heptanediamine'with acrylonitrile;9,9-dinitro-4,l4-diaza-l,l7-heptadecane dinitrile is prepared bycondensing 5,5-dinitro-1,9-nonane diamine with acrylonitrile;8,8-dinitro-4,13-diaza-1,16: hexadecane dinitrile is prepared byreacting 4,4-dinitro- 1,8-octanediamine with acrylonitrile; and7,7-dinitro-4,11- diaza-1,l4-tetradecane dinitrile is prepared byreacting 3,3-dinitro-l,6-diamine with acrylonitrile. Any member of theentire disclosed class of compounds can be prepared simply by condensingan appropriate geminal dinitro diamine with acrylonitrile in accordancewith the teachings of this invention. v

This application is a continuation-in-part of our copending applicationNo. 439,467, filed June 25, 1954.

We claim: Y 1. As new compositions of matter thedinitro-diazadinitrile's'having the general formula:

wherein A and A are lower alkylene radicals.

2. As a new composition of matter, 7,7-dinitro-4,10-diaza-1,13-tridecane dinitrile having the structural formula:

3. As a new composition of matter, 8,8-dinitro-4,l2-diaza-1,15-pentadecane dinitrile having the structural formula:

a s 4 e diaza-1,l 7-heptadecane dinitrile having the structural 8. Themethod of claim 7 wherein the condensation formula: is conducted in thepresence of an inert organic solvent.

r NCe-OHzQHqNH-CH10H2CHaOHrfilfiHaGHaCHaCHgrfiQrCHzOHg-ON 5. As a newcomposition of matter, 8,8-dinitro-4,13 9. The method of preparing7,7-dinitro-4,10-diaza-l,13- i diaza-l,16-hexadecane dinitrile havingthe structural tridecane dinitrile which comprises condensing acryloniformula: V trile with 3,3-dinitro-L5-pentane diami ne.

6. As a newkornposition of matter, 7,7-dinitro-4,11- 15 10. The methodof preparing 8,8-dinitro-4,1 2-diazadiaza-lJQ-tetradecane dinitrilehaving the Structural LIS-pentadecane dinitrile which comprisescondensing formula: V acrylonitrilc with 4,4-dinitro-1,7-heptanediamine.

11. The method of preparing 9,9-dinitro-4,14-diaza-NCCH2CH2NECH2CH:.?CH:CHaQHa-NH-CHzGHrCN 1,17-heptadecane dinitrile whichcomprises condensing 20 acrylonitrile with 5,5-dinitro-1,9-nonane(ii-amine. 7. The method of preparing dinitro-diaza-dinitriles Themethod ?f PrePar ing 3 f F having the gemral formula; 5 1,16-hexadecanedlnltrrle which compr ses condensing I 7 N03 acrylonitrile with4,4-d1n1tro-1,8-octane dlamine.

' 13. The method of preparing '7,7-dinitro 4,ll-di aza- 251,l4-'tet1adecar1e dinitrile which comprises condensing t s Iacrylonitrile with 3,3-dinitro-l,6-diamine. which comprises condensingacrylomtr leyv th a dlrntro K diarnine alkane composition having thegeneral iormula: i N f ig d 3 wherein A and A are lower alkylenererdkeals.

1. AS NEW COMPOSITIONS OF MATTER THE DINITRO-DIAZADINITRILES HAVING THEGENERAL FORMULA: